CN114618564B - Catalyst for preparing glycollic acid by catalyzing carbonylation of formaldehyde with solid acid, preparation and application thereof - Google Patents
Catalyst for preparing glycollic acid by catalyzing carbonylation of formaldehyde with solid acid, preparation and application thereof Download PDFInfo
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses a preparation method and application of a catalyst for preparing glycollic acid by catalyzing formaldehyde with solid acid. The method is characterized in that a certain amount of heteropoly acid (salt) containing phosphorus (HPA) compound (HPA) and metal components such as Rh, pt, co and the like are introduced in situ in the preparation process of the multi-stage hole ZSM-5 molecular sieve, so that the heteropoly acid (salt) containing phosphorus and the nanometer components such as Rh, pt and Co are loaded on the surface of the multi-stage hole ZSM-5 molecular sieve. The catalyst (Rh-Pt-Co-HPA/ZSM-5) is used, paraformaldehyde, CO and water are used as reaction raw materials, and the reaction is carried out in a high-pressure reaction kettle for 1-8 hours under the reaction pressure of 0.5-5MPa and the reaction temperature of 60-150 ℃. Can realize the high-selectivity conversion of paraformaldehyde, CO and water into glycolic acid. The preparation method is easy to scale up. Can be applied to the field of formaldehyde carbonylation acid catalysis, and has better industrial application prospect.
Description
Technical Field
The invention relates to a preparation method and application of a catalyst for preparing glycollic acid by carbonylation of formaldehyde, belonging to the catalyst preparation technology in the technical field of industrial catalysis.
Background
With the increase of global environmental protection, china implements 'plastic limit orders' from 2008, and encourages popularization and application of degradable plastic substitute products. The polyglycolic acid has better gas barrier property, biocompatibility and degradability, so the polyglycolic acid has better application prospect in the fields of medical suture, tissue repair and the like. At present, the material is mainly formed by the polycondensation of glycolic acid, glycollate, glycolide and other raw materials. Glycolic acid, also known as glycolic acid, is the simplest aliphatic hydroxy acid.
In recent years, the research and development of polyglycolic acid technology in China are actively progressed. The method for preparing the glycolic acid mainly comprises a chemical method and a biological method, the glycolic acid product obtained by the biological method has high purity, but the cell culture period of the thallus is long, and a carbon source is required to be added to improve the fermentation efficiency, so that the industrialization is not realized. The chemical method mainly comprises an oxalic acid electro-reduction method, a glyoxal disproportionation method, a formaldehyde carbonylation method and the like. The formaldehyde carbonylation method using coal-based synthesis gas as raw material is developed rapidly, and accords with the resource characteristics of rich coal and little oil in China.
CN111039754A provides a method for preparing ethylene glycol from formaldehyde through glycollic acid, and the acid catalyst used for the formaldehyde carbonylation reaction is homogeneous catalyst such as sulfuric acid, phosphoric acid and nitric acid, and heterogeneous catalyst such as silicon-aluminum composite oxide, acid resin and molecular sieve. CN 111097540A discloses a catalyst for synthesizing methyl glycolate and a preparation method thereof, wherein the catalyst takes silicon dioxide and titanium dioxide as carriers, and fluorine-containing organic sulfonic acid strong acid is immobilized on the carriers by a sol-gel method. The catalyst is used for producing methyl glycolate, and has the characteristic of easy separation and recovery.
In conclusion, various solid acid catalysts have been developed, so that homogeneous catalysis and heterogenization are realized, and the advantages of easy product separation are achieved. However, compared with the homogeneous catalysts used in the existing industrial processes, the activity is still insufficient, and large-scale industrial application cannot be realized. In view of the above problems, the present inventors have developed a catalyst for the carbonylation of formaldehyde to produce glycolic acid. During the preparation of the hierarchical porous ZSM-5 molecular sieve, certain amount of heteropoly acid (salt) containing phosphorus (HPA) and metal components such as Rh, pt and Co are introduced in situ to make the heteropoly acid (salt) containing phosphorus and nanometer components such as Rh, pt and Co supported on the surface of the hierarchical porous ZSM-5 molecular sieve. In the carbonylation reaction process, rhodium and cobalt catalysts with phosphorus ligands are generated in situ, so that the activity of the carbonylation reaction is effectively improved. The platinum component is introduced to effectively inhibit the generation of carbon deposit and improve the reuse times of the catalyst. The preparation method is easy to amplify and can be applied to the field of acid catalysis such as formaldehyde carbonylation and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a solid acid catalyst for formaldehyde carbonylation, and the catalyst prepared by the method can effectively improve the carbonylation activity of the solid acid catalyst and improve the repeated use times of the catalyst.
The invention provides a preparation method of a glycolic acid Rh-Pt-Co-HPA/ZSM-5 catalyst prepared by catalyzing formaldehyde, which comprises the steps of firstly, dissolving tetrapropylammonium hydroxide into a solvent to prepare a solution with the concentration of 0.01-2.0mol/L, respectively adding tetraethoxysilane and amphiphilic organic silicon under the stirring condition, wherein the concentration of the tetraethoxysilane is 0.5-1.5mol/L, and the molar ratio of the tetraethoxysilane to the amphiphilic organic silicon is 20:1-100:1, adding a certain amount of aluminum nitrate according to the silicon-aluminum ratio of 30-150, and adding ammonia water (the mass concentration is 25%) to adjust the pH value to 8-10; stirring for 30-120 min at 35-60 deg.C, adding heteropoly phosphatic heteropoly acid (salt), rhodium salt, platinum salt and cobalt macromolecular heterocyclic compound, stirring for 1-12h, transferring into stainless steel crystallization kettle, crystallizing for 12-72h at 100-250 deg.C, filtering, drying, and roasting at 400-600 deg.C to remove tetrapropylammonium hydroxide to obtain Rh-Pt-Co-HPA/ZSM-5 catalyst.
The invention provides a preparation method of a catalyst for preparing glycolic acid Rh-Pt-Co-HPA/ZSM-5 by catalyzing formaldehyde, which is characterized by comprising the following steps: the loading capacity of the phosphoheteropoly acid (salt) (counted by phosphorus pentoxide) in the Rh-Pt-Co-HPA/ZSM-5 catalyst is 5 to 40 percent, the loading capacity of rhodium metal is 0.01 to 2 percent, the loading capacity of platinum is 0.01 to 5 percent, and the loading capacity of cobalt is 0.5 to 20 percent.
The heteropoly acid (salt) is one or more than two of phosphomolybdic heteropoly acid, phosphotungstic heteropoly acid quaternary ammonium salt and the heteropoly acid (salt), and the heteropoly acid and the salt are both Keggin type structures.
The amphiphilic organosilicon is a twelve-carbon long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 12 H 25 ) Fourteen carbon long organosilanes ((CH) 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 14 H 29 ) Sixteen carbon long organosilanes ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Octadecylsilyl ((CH) 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 18 H 37 ) One or more than two of them.
The rhodium salt is one or more of chlororhodic acid, ammonium chlororhodate, sodium chlororhodate, rhodium nitrate, rhodium trichloride hydrate, tris (triphenylphosphine) rhodium chloride, ammonium hexanitrorhodate, rhodium octanoate dimer, rhodium acetate dimer, hexadecanehexarhodium, tetradecanetetrarhodium
The platinum salt is one or more of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, dinitro tetraammonium platinum, hexahydroxyplatinic acid, sodium hexahydroxyplatinate, tetranitro potassium platinate, tetrakis (triphenylphosphine) platinum, potassium di (oxalate) platinum and diiodo diammonium platinum.
The macromolecular heterocyclic compound of cobalt is one or more of cobalt porphyrin, cobalt phthalocyanine, cobalt naphthalocyanine and cobalt spiro cyanine.
The application of the catalyst in the formaldehyde carbonylation reaction; the specific reaction conditions are that paraformaldehyde, CO and water are used as reaction raw materials, and the reaction is carried out in a high-pressure reaction kettle for 1-8h under the reaction pressure of 0.5-5MPa and the reaction temperature of 60-150 ℃.
Compared with the prior art, the invention has the following advantages:
the catalyst prepared by the method generates the rhodium and cobalt catalysts with the phosphorus ligands in situ in the carbonylation reaction process, thereby effectively improving the activity of the carbonylation reaction. The platinum component is introduced to effectively inhibit the generation of carbon deposit and improve the reuse times of the catalyst. The preparation method is easy to amplify and can be applied to the field of acid catalysis such as formaldehyde carbonylation and the like.
Detailed Description
Example 1:
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing at 35 ℃ for 2h, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25 percent, the same below) to adjust the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5 percentAdding rhodium nitrate according to the loading of 0.5 percent of rhodium, adding cobalt porphyrin according to the loading of 2 percent of cobalt, adding phosphotungstic acid according to the loading of 10 percent of phosphorus pentoxide, continuously stirring for 2 hours, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at 200 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove a tetrapropylammonium hydroxide template agent, thereby obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst capable of catalyzing formaldehyde to prepare glycolic acid.
Comparative example 1:
50.7mL of tetraethylorthosilicate, 2.5mL of a sixteen carbon long organosilane quaternary ammonium salt ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL of 0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium platinochloride according to the platinum loading of 0.5%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 24h at 200 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Thus obtaining the Pt-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Comparative example 2:
adding 50.7mL of ethyl orthosilicate and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%) to adjust the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 24h at 200 ℃, filtering, drying, roasting at 500 ℃ to remove tetrapropylammonium hydroxide template agent, and obtaining Rh-Pt-Co-HPA/ZSM-5 catalyst capable of catalyzing formaldehyde to prepare glycolic acid
Example 2: type and loading capacity of heteropoly acid (salt)
50.7mL of tetraethoxysilane and 2.5mL of decaSix carbon long organosilanes ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 40%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration, drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 3: type and loading capacity of heteropoly acid (salt)
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphomolybdic acid according to the phosphorus pentoxide loading of 5%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 150 ℃, performing suction filtration, drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 4: long chain organosilicon species
50.7mL of ethyl orthosilicate, 2.5mL of dodecane long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 12 H 25 ) Adding into a 500mL round bottom flask with 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, stirring and hydrolyzing at 35 ℃ for 2h, and adding Si/Al =Adding aluminum nitrate 50, adding ammonia water (mass concentration is 25%), adjusting the pH value to 10, stirring for 30 minutes, adding potassium platinochloride according to the platinum loading of 0.5%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuously stirring for 2 hours, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72 hours at 250 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 5: long chain organosilicon species
50.7mL of ethyl orthosilicate, 2.5mL of octadecylsilyl ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 18 H 37 ) Adding the mixture and a tetrapropylammonium hydroxide aqueous solution of 200mL0.5mol/L into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuing stirring for 2h, transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration, drying, and roasting at 500 ℃ to remove a tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 6: platinum salt species and loading
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25 percent) to adjust the pH value to 10, stirring for 30 min, adding chloroplatinic acid according to the platinum loading of 0.2 percent, adding rhodium nitrate according to the rhodium loading of 0.5 percent, adding cobalt porphyrin according to the cobalt loading of 2 percent, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10 percent, continuously stirring for 2h, and adding the mixture with the mixture along with the weight of the tetrapropylammonium hydroxide aqueous solution of 200mL0.5mol/L tetrapropylammonium hydroxideThen transferring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72 hours at 250 ℃, filtering, drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 7: platinum salt species and loading
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding sodium chloroplatinate according to the 10% platinum loading capacity, adding rhodium nitrate according to the 0.5% rhodium loading capacity, adding cobalt porphyrin according to the 2% cobalt loading capacity, adding phosphotungstic acid according to the 10% phosphorus pentoxide loading capacity, continuing stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, filtering, drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 8: cobalt macromolecular compound species and loading capacity
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to 0.5% platinum loading, adding rhodium nitrate according to 0.5% rhodium loading, adding cobalt phthalocyanine according to 20% cobalt loading, adding phosphotungstic acid according to 10% phosphorus pentoxide loading, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration, drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 9: cobalt macromolecular heterocyclic compound species and loading capacity
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 15%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 0.5%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration, drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent. Obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst which can catalyze formaldehyde to prepare glycollic acid.
Example 10: rhodium salt species and loadings
50.7mL of ethyl orthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5%, adding tris (triphenylphosphine) rhodium chloride according to the rhodium loading of 0.01%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent, thereby obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst capable of catalyzing formaldehyde to prepare glycolic acid.
Example 11: rhodium salt species and loading
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixed solution and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =50, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 10, stirring for 30 min, adding potassium platinochloride according to the platinum loading of 0.5%, adding ammonium chlororhodate according to the rhodium loading of 2%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, stirring for 2h, transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove the tetrapropylammonium hydroxide template agent, thereby obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst capable of catalyzing formaldehyde to prepare glycollic acid.
Example 12: different silicon to aluminium ratio (Si/Al = 30)
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding the mixture and 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 500mL round-bottom flask, stirring and hydrolyzing for 2h at 35 ℃, adding aluminum nitrate according to Si/Al =30, adding ammonia water (the mass concentration is 25%), adjusting the pH value to 8, stirring for 30 min, adding potassium chloroplatinite according to the platinum loading of 0.5%, adding rhodium nitrate according to the rhodium loading of 0.5%, adding cobalt porphyrin according to the cobalt loading of 2%, adding phosphotungstic acid according to the phosphorus pentoxide loading of 10%, continuously stirring for 2h, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72h at 250 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove tetrapropylammonium hydroxide template agent, thereby obtaining the Rh-Pt-Co-HPA/ZSM-5 catalyst capable of catalyzing formaldehyde to prepare glycolic acid.
Example 13: different silicon to aluminium ratio (Si/Al = 150)
50.7mL of tetraethylorthosilicate, 2.5mL of hexadecane-long organosilane ((CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 ) Adding into a 500mL round bottom flask with 200mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, hydrolyzing under stirring at 35 deg.C for 2h, adding aluminum nitrate according to Si/Al =150, adding ammonia water (25 wt%) to adjust pH to 10, stirring for 30 min, and adding into a 0.5%Adding potassium chloroplatinite in platinum loading capacity, adding rhodium nitrate in 0.5% of rhodium loading capacity, adding cobalt porphyrin in 2% of cobalt loading capacity, adding phosphotungstic acid in 10% of phosphorus pentoxide loading capacity, continuously stirring for 2 hours, then transferring into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, crystallizing for 72 hours at 100 ℃, performing suction filtration and drying, and roasting at 500 ℃ to remove tetrapropylammonium hydroxide template agent to obtain the Rh-Pt-Co-HPA/ZSM-5 catalyst capable of catalyzing formaldehyde to prepare glycolic acid.
The catalysts obtained in example 1, comparative example 2, and examples 3, 5, 7, 9, 11, and 13 were evaluated for their methanol amination performance under the following reaction conditions: reacting paraformaldehyde, CO and water serving as reaction raw materials in a high-pressure reaction kettle for 6 hours at the reaction pressure of 2.5MPa and the reaction temperature of 90 DEG C
Claims (10)
1. A preparation method of a catalyst for catalyzing formaldehyde to prepare glycolic acid Rh-Pt-Co-HPA/ZSM-5 is characterized by comprising the following steps: firstly, dissolving tetrapropylammonium hydroxide into a solvent to prepare a solution with the concentration of 0.01-2.0mol/L, respectively adding tetraethoxysilane and amphiphilic organic silicon under the stirring condition, wherein the concentration of the tetraethoxysilane is 0.5-1.5mol/L, and the molar ratio of the tetraethoxysilane to the amphiphilic organic silicon is 20:1-100:1, adding a certain amount of aluminum nitrate according to the silicon-aluminum ratio of 30-150; adding 25-28% by mass of concentrated ammonia water to adjust the pH value to 8-10, stirring for 30-120 minutes at 35-60 ℃, then adding heteropoly acid and/or heteropoly acid salt containing phosphorus, rhodium salt, platinum salt and cobalt macromolecular heterocyclic compound, continuously stirring for 1-12h, then transferring into a crystallization kettle, crystallizing for 12-72h at 100-250 ℃, performing suction filtration and drying, and roasting at 400-600 ℃ to remove tetrapropylammonium hydroxide to obtain the Rh-Pt-Co-HPA/ZSM-5 catalyst.
2. The method of claim 1, wherein: based on the mass content, the loading capacity of the heteropoly phosphatic heteropoly acid and/or the heteropoly phosphatic heteropoly acid salt roasting product in the Rh-Pt-Co-HPA/ZSM-5 catalyst is 5 to 40 percent, the loading capacity of rhodium metal is 0.01 to 2 percent, the loading capacity of platinum is 0.01 to 5 percent and the loading capacity of cobalt is 0.5 to 20 percent, which are calculated by phosphorus pentoxide.
3. The method of claim 1, wherein: the heteropoly acid and/or the phosphorus-containing heteropoly acid salt is one or more than two of phosphomolybdic heteropoly acid, phosphotungstic heteropoly acid, phosphomolybdic heteropoly acid quaternary ammonium salt and phosphotungstic heteropoly acid quaternary ammonium salt, and the heteropoly acid and the phosphorus-containing heteropoly acid salt are both Keggin type structures.
4. The method of claim 1, wherein: the amphiphilic organosilicon is a long-twelve-carbon organosilane (CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 12 H 25 Fourteen carbon long organosilanes (CH) 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 14 H 29 Sixteen carbon long organosilanes (CH) 3 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 16 H 33 Octadecylsilylene (CH) 3 CH 2 O) 3 SiC 3 H 6 N(CH 3 ) 2 C 18 H 37 One or more than two of them.
5. The method of claim 1, wherein: the rhodium salt is one or more of chlororhodic acid, chlororhodic acid ammonium, chlororhodic acid sodium, rhodium nitrate, rhodium trichloride hydrate, tris (triphenylphosphine) rhodium chloride, hexanitro ammonium rhodate, octanoic acid rhodium dimer, acetic acid rhodium dimer, hexadecacarbonyl hexarhodium and tetradecacarbonyl tetrarhodium.
6. The method of claim 1, wherein: the platinum salt is one or more of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, dinitro tetraammonium platinum, hexahydroxyplatinic acid, sodium hexahydroxyplatinate, tetranitro potassium platinate, tetrakis (triphenylphosphine) platinum, potassium di (oxalate) platinum and diiodo diammonium platinum.
7. The method of claim 1, wherein: the macromolecular heterocyclic compound of cobalt is one or more of cobalt porphyrin, cobalt phthalocyanine, cobalt naphthalocyanine and cobalt spiro cyanine.
8. A variable loading Rh-Pt-Co-HPA/ZSM-5 catalyst obtained by the method of preparation of claim 1.
9. Use of a catalyst according to claim 8, wherein:
the catalyst is used in a formaldehyde carbonylation reaction.
10. Use according to claim 9, characterized in that:
the specific reaction conditions are that paraformaldehyde, CO and water are used as reaction raw materials, the reaction pressure is 0.5-5MPa, the reaction temperature is 60-150 ℃, and the reaction is carried out in a high-pressure reaction kettle for 1-8h.
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